U.S. patent application number 10/022118 was filed with the patent office on 2003-08-07 for fluorochemical urethane composition for treatment of fibrous substrates.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Buckanin, Richard S., Cote', Linda G., Johnson, Mitchell T., Lien, Larry A..
Application Number | 20030149218 10/022118 |
Document ID | / |
Family ID | 21807901 |
Filed Date | 2003-08-07 |
United States Patent
Application |
20030149218 |
Kind Code |
A1 |
Cote', Linda G. ; et
al. |
August 7, 2003 |
Fluorochemical urethane composition for treatment of fibrous
substrates
Abstract
Fluorochemical urethane compositions comprising one or more
fluorochemical urethane compounds, and one or more auxiliary
compounds for treatment of a fibrous substrate are described. The
fluorochemical compositions are capable of improving one or more of
the oil- and/or water repellency, stain- and/or soil repellency and
stain and/or soil release properties, with improved durability, of
the fibrous substrate treated with the fluorochemical
composition.
Inventors: |
Cote', Linda G.; (Woodbury,
MN) ; Johnson, Mitchell T.; (Saint Paul, MN) ;
Lien, Larry A.; (Forest Lake, MN) ; Buckanin, Richard
S.; (Woodbury, MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
21807901 |
Appl. No.: |
10/022118 |
Filed: |
December 17, 2001 |
Current U.S.
Class: |
528/77 |
Current CPC
Class: |
C08G 18/8077 20130101;
C08G 18/283 20130101; C08G 18/4833 20130101; Y10T 428/2938
20150115; Y10T 428/2962 20150115; Y10T 428/31551 20150401; Y10T
428/31591 20150401; C08G 18/289 20130101; C09D 175/04 20130101;
C08G 18/2885 20130101; Y10T 428/2933 20150115 |
Class at
Publication: |
528/77 |
International
Class: |
C08G 018/32 |
Claims
What is claimed is:
1. A chemical composition comprising: (a) a first component
comprising one or more urethane comprising the reaction product of:
(1) one or more polyfunctional isocyanate compounds; (2) one or
more hydrophilic polyoxyalkylene compounds; (3) one or more silane
compounds of the formula:X--R.sup.1--Si--(Y).sub.3 wherein X is
--NH.sub.2; --SH; --OH; --N.dbd.C.dbd.O; or --NRH where R is
selected from the group consisting of phenyl, straight and branched
aliphatic, alicyclic, and aliphatic ester groups; R.sup.1 is an
alkylene, heteroalkylene, aralkylene, or heteroaralkylene group;
and each Y is independently a hydroxyl; a hydrolyzable moiety
selected from the group consisting of alkoxy, acyloxy,
heteroalkyoxy, heteroacyloxy, halo, and oxime; or a
non-hydrolyzable moiety selected from the group consisting of
phenyl, alicyclic, straight-chain aliphatic, and branched-chain
aliphatic, wherein at least one Y is a hydrolyzable moiety; and (4)
one or more fluorochemical monofunctional compound; and (b) a
second component comprising one or more hydrophilic auxiliary
compounds capable of further improving the oil- and/or water
repellency or soil/stain release properties of a fibrous substrate
treated with the fluorochemical urethane compounds.
2. The chemical composition of claim 1 wherein the polyfunctional
isocyanate compound of said first component is a diisocyanate or
triisocyanate.
3. The chemical composition of claim 1 wherein the fluorochemical
monofunctional compound of said first component is of the
formula:R.sub.f--Z--R.sup.2--Xwherein: R.sub.f is a perfluoroalkyl
group or a perfluoroheteroalkyl group; Z is a connecting group
selected from a covalent bond, a sulfonamido group, a carboxamido
group, a carboxyl group, or a sulfonyl group; and R.sup.2 is a
divalent straight or branched chain alkylene, cycloalkylene, or
heteroalkylene group of 1 to 14 carbon atoms; and X is --NH.sub.2;
--SH; --OH; --N.dbd.C.dbd.O; or --NRH where R is selected from the
group consisting of phenyl, straight and branched aliphatic,
alicyclic, and aliphatic ester groups; R.sup.1 is an alkylene,
heteroalkylene, aralkylene, or heteroaralkylene group.
4. The chemical composition of claim 3 wherein R.sub.f is a
perfluoroalkyl group of 2 to 12 carbons.
5. The chemical composition of claim 3 wherein R.sub.f is a
perfluoroalkyl group of 3 to 5 carbons.
6. The composition of claim 1 wherein said first component
polyoxyalkylene compounds are homo-and copolymers of
polyoxyethylene and polyoxypropylene.
7. The composition of claim 1 wherein said second auxiliary
component is the reaction product of a polyisocyanate, a blocking
agent and a polyoxyalkylene compound.
8. The composition of claim 7 wherein said isocyanate groups of
said second component polyisocyanate are blocked isocyanate
groups.
9. The composition of claim 8 wherein said blocked isocyanate
groups are prepared by a thermally reversible reaction with
phenols, lactams, and oximes.
10. The composition of claim 7 wherein said polyoxyalkylene
compounds of said second component are homo- and copolymers of
polyoxyethylene, polyoxypropylene, polyoxytetramethylene.
11. The composition of claim 1 wherein the amount of said
hydrophilic polyoxyalkylene compounds of said first component is
sufficient to react with between 0.1 and 30% of available
isocyanate groups, the amount of said silane compounds is
sufficient to react with between 0.1 and 25% of available
isocyanate groups, and the amount of said fluorochemical
monofunctional compounds is sufficient to react with between 60 and
90% of available isocyanate groups of said urethane compounds.
12. The composition of claim 1 wherein the amount of said
polyoxyalkylene compound of said second component is such that from
about 25 to about 75% of the available isocyanate groups of said
auxiliary compound are reacted.
13. The composition of claim 12 wherein the unreacted isocyanate
groups are blocked isocyanate groups.
14. The composition of claim 1 wherein the ratio of said first
component urethane compound to said second auxiliary compound is
from 12:1 to 1:12.
15. The composition of claim 1 wherein the ratio of said first
component urethane compound to said second auxiliary compound is
from 3:1 to 6:1.
16. The composition of claim 1 wherein said polyoxyalkylene
compound of said first component has a functionality of greater
than 1.
17. The composition of claim 7 wherein said polyoxyalkylene
compound of said second component has a functionality of one.
18. A treatment composition comprising a solution of the chemical
composition of claim 1 and a solvent.
19. The treatment composition of claim 18 wherein the solvent is
selected from the group consisting of water, an organic solvent,
and mixtures thereof.
20. The treatment composition of claim 18 comprising from about 0.1
to about 50 percent chemical composition.
21. An article comprising a substrate having a cured coating
derived from at least one solvent and a chemical composition of
claim 1.
22. The article of claim 21 wherein said substrate is a fibrous
substrate.
23. A method for imparting stain-release characteristics to a
substrate comprising the steps of applying the treatment
composition of claim 1, and allowing the coating composition to
cure.
24. The method of claim 23 wherein said substrate is a fibrous
substrate
25. The method of claim 24 wherein said coating composition is
applied in an amount sufficient to provide between 0.05% and 5%
solids on fiber.
26. The method of claim 24 wherein said composition is cured at
ambient temperature.
27. A method for imparting stain-release characteristics to a
fibrous substrate comprising the steps of: (a) applying a coating
composition of claim 13, and. (b) curing the coating composition at
elevated temperature to deblock said blocked isocyanate groups.
Description
FIELD OF THE INVENTION
[0001] This invention relates to chemical compositions comprising
one or more fluorochemical urethane compounds, and one or more
auxiliary compounds for treatment of a fibrous substrate. The
invention further relates of fluorochemical coating compositions
comprising at least one solvent and the chemical compositions of
the present invention. The fluorochemical compositions are capable
of improving one or more of the oil- and/or water repellency,
stain- and/or soil repellency and stain and/or soil release
properties, with improved durability, to the fibrous substrate
treated with the fluorochemical composition. This invention also
relates to articles comprising a fibrous substrate and on this
substrate is a cured coating derived from the coating compositions
of the present invention. The cured coating resists being worn-off
due to wear, abrasion and cleaning. In another aspect, this
invention relates to a process for imparting stain-release
characteristics to substrates.
BACKGROUND OF THE INVENTION
[0002] The use of certain fluorochemical compositions on fibers and
fibrous substrates, such as textiles, paper, and leather, to impart
oil- and water-repellency and soil- and stain-resistance is well
known in the art. See, for example, Banks, Ed., Organofluorine
Chemicals and Their Industrial Applications, Ellis Horwood Ltd.,
Chichester, England, 1979, pp. 226-234. Such fluorochemical
compositions include, for example, fluorochemical guanidines (U.S.
Pat. No. 4,540,497, Chang et al.), compositions of cationic and
non-cationic fluorochemicals (U.S. Pat. No. 4,566,981, Howells),
compositions containing fluorochemical carboxylic acid and epoxidic
cationic resin (U.S. Pat. No. 4,426,466, Schwartz), fluoroaliphatic
carbodiimides (U.S. Pat. No. 4,215,205, Landucci), fluoroaliphatic
alcohols (U.S. Pat. No. 4,468,527, Patel), fluorine-containing
addition polymers, copolymers, and macromers (U.S. Pat. Nos.
2,803,615; 3,068,187; 3,102,103; 3,341,497; 3,574,791; 3,916,053;
4,529,658; 5,216,097; 5,276,175; 5,725,789; 6,037,429),
fluorine-containing phosphate esters (U.S. Pat. Nos. 3,094,547;
5,414,102; 5,424,474), fluorine-containing urethanes (U.S. Pat.
Nos. 3,987,182; 3,987,227; 4,504,401; 4,958,039), fluorochemical
allophanates (U.S. Pat. Nos. 4,606,737) fluorochemical biurets
(U.S. Pat. Nos. 4,668,406), fluorochemical oxazolidinones (U.S.
Pat. No. 5,025,052), and fluorochemical piperazines (U.S. Pat. No.
5,451,622).
[0003] As indicated above, both solvent and water based
fluorochemical compositions have been used to provide water- and
oil-repellency to fibrous surfaces. Since organic solvents pose
health, safety, and environmental concerns, the water-based
compositions are particularly desirable. However, the previously
known compositions are typically aqueous dispersions or emulsions,
not solutions; therefore, may require a high temperature cure to
impart good repellency properties. In many cases, for example, high
temperature curing is not practical or possible. For this reason
there is a continuing need for urethanes that do not require costly
and energy consuming high temperature cure conditions to impart
good repellency properties. Therefore, urethane compositions,
including those containing fluorine, that display increased water
solubility are needed to eliminate the need for high temperature
cure conditions, as well as to increase the ease of preparation and
to provide more stable aqueous solutions.
SUMMARY OF THE INVENTION
[0004] The inventors recognized the need for fluorochemical
compositions that can successfully impart one or more of the
following uniform, durable properties: oil- and water-repellency
and/or soil- and stain-resistance and/or soil- and
stain-repellency. These chemical compositions may be water and/or
organic solvent soluble and may not require high temperatures for
curing.
[0005] In one aspect, this invention relates to chemical
compositions comprising one or more fluorochemical urethane
compounds, and one or more auxiliary compounds capable of further
improving the soil- and/or stain release and oil- and/or water
repellency of a fibrous substrate. These urethane compounds
comprise the reaction product of (a) one or more polyfunctional
isocyanate compounds; (b) one or more hydrophilic polyoxyalkylene
compounds; (c) one or more fluorochemical monofunctional compounds;
and (d) one or more isocyanate-reactive silanes.
[0006] As used herein, the term "fluorochemical urethane compound"
means a compound derived or derivable from the reaction of at least
one polyfunctional isocyanate compound and at least one hydrophilic
polyoxyalkylene compound, one or more fluorinated monofunctional
compounds; and (ii) one or more isocyanate-reactive silane
compounds.
[0007] The chemical compositions of the present invention,
comprising one or more urethane compounds, impart one or more of
release, repellency and resistance characteristics to oil, water,
stains and soils, and exhibit durability (i.e. they resist being
worn-off) when exposed to wear and abrasion from use, cleaning, and
the elements. Therefore, these compositions can be applied as
coatings to a wide variety of substrates, for example, by topical
application, to impart durable release/repellency/resistant
properties to the substrates. When applied as a coating, the
chemical compositions of the present invention can provide uniform
properties to a fibrous substrate and do not change the appearance
of the substrate to which they are applied. Even though the
urethane compounds are of relatively low fluorochemical content,
the chemical compositions of the present invention provide durable
stain-release properties comparable to or better than those of the
prior art. In addition, with some embodiments, the chemical
compositions of the present invention do not require high
temperature curing; they can be cured (i.e., dried) at ambient
temperature.
[0008] Certain preferred embodiments of the chemical compositions
of the present invention include those compositions comprising
terminal fluorochemical groups having from two to twelve carbons,
preferably from three to six carbons, and more preferably four
carbons. Even with R.sub.f groups that are relatively short (i.e.
six or fewer carbons), these chemical compositions, surprisingly,
exhibit excellent release/resistance/repellency. Although
compositions comprising lower fluorine content are less expensive,
those of skill in the art have typically overlooked R.sub.f groups
shorter than eight carbons because they have been known to impart
inferior oil- and water-repellency and stain resistance.
[0009] Many previously known fluorochemical surfactants contain
perfluorooctyl moieties. These surfactants ultimately degrade to
perfluorooctyl-containing compounds. It has been reported that
certain perfluorooctyl-containing compounds may tend to
bio-accumulate in living organisms; this tendency has been cited as
a potential concern regarding some fluorochemical compounds. For
example, see U.S. Pat. No. 5,688,884 (Baker et al.). As a result,
there is a desire for fluorine-containing compositions which are
effective in providing desired release/resistance/repellency
properties, and which eliminate more effectively from the body
(including the tendency of the composition and its degradation
products).
[0010] It is expected that the preferred fluorochemical
compositions of the present invention, which contain perfluoroalkyl
C.sub.3 to C.sub.6 moieties, when exposed to biologic, thermal,
oxidative, hydrolytic, and photolytic conditions found in the
environment, will break down to various degradation products. For
example, compositions comprising perfluorobutylsulfonamido moieties
are expected to degrade, at least to some extent, ultimately to
perfluorobutylsulfonate salts. It has been surprisingly found that
perfluorobutylsulfonate, tested in the form of its potassium salt,
eliminates from the body much more effectively than
perfluorohexylsulfonate and even more effectively than
perfluorooctylsulfonate.
[0011] Another embodiment of the present invention relates to a
composition for treatment of fibrous substrates comprising a
solution of the chemical composition of the present invention and a
solvent. In this embodiment, it is important that the chemical
composition be dissolved in the solvent. When applied to a
substrate, this treatment composition provides a uniform
distribution of the chemical composition on the substrate without
altering the appearance of the substrate. With some embodiments a
high temperature cure is not required to provide this coating; the
treatment composition can be cured (i.e. dried) at ambient
temperatures. In other embodiments a high temperature cure (e.g.
temperatures in above about 125.degree. F. or 49.degree. C.) may be
used with coating compositions of the invention.
[0012] This invention also relates to an article comprising a
fibrous substrate having a cured coating derived from at least one
solvent and a chemical composition of the present invention. After
application and curing of the chemical composition, the substrate
displays durable release/resistance/repellency properties.
[0013] This invention further relates to a method for imparting
stain-release characteristics to a fibrous substrate, having one or
more surfaces, comprising the steps of:
[0014] (a) applying the coating composition of the present
invention onto one or more surfaces of the substrate and
[0015] (b) allowing the coating composition to cure (i.e. dry).
DEFINITIONS
[0016] Unless otherwise stated, the following terms used in the
specification and claims have the meanings given below:
[0017] "Acyloxy" means a radical --OC(O)R where R is, alkyl,
alkenyl, and cycloalkyl, e.g., acetoxy, 3,3,3-trifluoroacetoxy,
propionyloxy, and the like.
[0018] "Alkoxy" means a radical --OR where R is an alkyl group as
defined below, e.g., methoxy, ethoxy, propoxy, butoxy, and the
like.
[0019] "Alkyl" means a linear saturated monovalent hydrocarbon
radical having from one to about twelve carbon atoms or a branched
saturated monovalent hydrocarbon radical having from three to about
twelve carbon atoms, e.g., methyl, ethyl, 1-propyl, 2-propyl,
pentyl, and the like.
[0020] "Alkylene" means a linear saturated divalent hydrocarbon
radical having from one to about twelve carbon atoms or a branched
saturated divalent hydrocarbon radical having from three to about
twelve carbon atoms, e.g., methylene, ethylene, propylene,
2-methylpropylene, pentylene, hexylene, and the like.
[0021] "Aryl aliphatic" means an alkylene radical defined above
with an aromatic group attached to the alkylene radical, e.g.,
benzyl, pyridylmethyl, 1-naphthylethyl, and the like.
[0022] "Cured chemical composition" means that the chemical
composition is dried or solvent has evaporated from the chemical
composition at ambient temperature (15-35.degree. C.) for up to
approximately 24 hours or at elevated temperature until
dryness.
[0023] "Fibrous substrate" means materials comprised of synthetic
fibers such as wovens, knits, nonwovens, carpets, and other
textiles; and materials comprised of natural fibers such as cotton,
paper, and leather.
[0024] "Fluorocarbon monofunctional compound" means a compound
having one isocyanate-reactive functional group and a
perfluoroalkyl or a perfluoroheteralkyl group, e.g.
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2- CH.sub.2OH,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2NH.sub.2,
C.sub.4F.sub.9CH.sub.2CH.sub.2OH, C.sub.4F.sub.9CH.sub.2CH.sub.2SH,
C.sub.2F.sub.5O(C.sub.2F.sub.4O).sub.3CF.sub.2CONHC.sub.2H.sub.4OH,
C.sub.2F.sub.5O(C.sub.2F.sub.4O).sub.3CF.sub.2CONHC.sub.2H.sub.4CO.sub.2H-
, C.sub.6F.sub.13CH.sub.2OH, C6F13CH2N(CH.sub.3)OH, and the
like.
[0025] "Heteroacyloxy" has essentially the meaning given above for
acyloxy except that one or more heteroatoms (i.e. oxygen, sulfur,
and/or nitrogen) may be present in the R group and the total number
of carbon atoms present may be up to 50, e.g.,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2C(O- )O--,
C.sub.4H.sub.9OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2C(O)O--,
CH.sub.3O(CH.sub.2CH.sub.2O).sub.nCH.sub.2CH.sub.2C(O)O--, and the
like.
[0026] "Heteroalkoxy" has essentially the meaning given above for
alkoxy except that one or more heteroatoms (i.e. oxygen, sulfur,
and/or nitrogen) may be present in the alkyl chain and the total
number of carbon atoms present may be up to 50, e.g.
CH.sub.3CH.sub.2OCH.sub.2CH.su- b.2O--,
C.sub.4H.sub.9OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2O--,
CH.sub.3O(CH.sub.2CH.sub.2O).sub.nH, and the like.
[0027] "Heteroalkyl" has essentially the meaning given above for
alkyl except that one or more catenary heteroatoms (i.e. oxygen,
sulfur, and/or nitrogen) may be present in the alkyl chain, these
heteroatoms being separated from each other by at least one carbon,
e.g., CH.sub.3CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OCH- (CH.sub.3)CH.sub.2--,
C.sub.4F.sub.9CH.sub.2CH.sub.2SCH.sub.2CH.sub.2--, and the
like.
[0028] "Heteroalkylene" has essentially the meaning given above for
alkylene except that one or more catenary heteroatoms (i.e. oxygen,
sulfur, and/or nitrogen) may be present in the alkylene chain,
these heteroatoms being separated from each other by at least one
carbon, e.g., --CH.sub.2OCH.sub.2O--,
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2N(CH.sub.3) CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2SCH.s- ub.2CH.sub.2--, and the like.
[0029] "Heteroaralkylene" means an aralkylene radical defined above
except that catenary oxygen, sulfur, and/or nitrogen atoms may be
present, e.g., phenyleneoxymethyl, phenyleneoxyethyl,
benzyleneoxymethyl, and the like.
[0030] "Halo" means fluoro, chioro, bromo, or iodo, preferably
fluoro and chloro.
[0031] "Isocyanate-reactive functional group" means a functional
group that is capable of reacting with an isocyanate group, such as
hydroxyl, amino, thiol, etc.
[0032] "Perfluoroalkyl" has essentially the meaning given above for
"alkyl" except that all or essentially all of the hydrogen atoms of
the alkyl radical are replaced by fluorine atoms and the number of
carbon atoms is from 2 to about 12, e.g. perfluoropropyl,
perfluorobutyl, perfluorooctyl, and the like.
[0033] "Perfluoroalkylene" has essentially the meaning given above
for "alkylene" except that all or essentially all of the hydrogen
atoms of the alkylene radical are replaced by fluorine atoms, e.g.,
perfluoropropylene, periluorobutylene, perfluorooctylene, and the
like
[0034] "Perfluoroheteroalkyl" has essentially the meaning given
above for "heteroalkyl" except that all or essentially all of the
hydrogen atoms of the heteroalkyl radical are replaced by fluorine
atoms and the number of carbon atoms is from 3 to about 100, e.g.
CF.sub.3CF.sub.2OCF.sub.2CF.sub- .2--,
CF.sub.3CF.sub.2O(CF.sub.2CF.sub.2O).sub.3CF.sub.2CF.sub.2--,
C.sub.3F.sub.7O(CF(CF.sub.3)CF.sub.2O).sub.mCF(CF.sub.3)CF.sub.2--where
m is from about 10 to about 30, and the like.
[0035] "Perfluoroheteroalkylene" has essentially the meaning given
above for "heteroalkylene" except that all or essentially all of
the hydrogen atoms of the heteroalkylene radical are replaced by
fluorine atoms, and the number of carbon atoms is from 3 to about
100, e.g., --CF.sub.2OCF.sub.2--,
--CF.sub.2O(CF.sub.2O).sub.n(CF.sub.2CF.sub.2O).su- b.mCF.sub.2--,
and the like.
[0036] "Perfluorinated group" means an organic group wherein all or
essentially all of the carbon bonded hydrogen atoms are replaced
with fluorine atoms, e.g. perfluoroalkyl, perfluoroheteroalkyl, and
the like.
[0037] "Polyisocyanate compound" means a compound containing two or
more isocyanate radicals, --NCO, attached to a multivalent organic
group, e.g. hexamethylene diisocyanate, the biuret and iscyanurate
of hexamethylene diisocyanate, and the like.
[0038] "Reactive polyoxyalkylene" means a polymer having
oxyalkylene repeat units with an average of 1 or more
isocyanate-reactive functional groups per molecule.
[0039] "Silane group" means a group comprising silicon to which at
least one hydrolyzable group is bonded, e.g. --Si(OCH.sub.3).sub.3,
--Si(OOCCH.sub.3).sub.2CH.sub.3, --Si(Cl).sub.3, and the like.
[0040] "Repellency" is a measure of a treated substrate's
resistance to wetting by oil and/or water and or adhesion of
particulate soil. Repellency may be measured by the test methods
described herein.
[0041] "Resistance" is the context or soiling or staining is a
measure of the treated substrate's ability to avoid staining and/or
soiling when contacted by stain or soil respectively.
[0042] "Release" is a measure of the treated substrate's ability to
have soil and/or stain removed by cleaning or laundering.
[0043] "Release/resistance/repellency" means the composition
demonstrates at least one of oil repellency, water repellency,
stain release, stain repellency, soil release and soil
repellency.
DETAILED DESCRIPTION OF THE INVENTION
[0044] The chemical compositions of the present invention comprise
one or more fluorochemical urethane compounds and one or more
auxiliary agents capable of further improving the
resistance/release/repellency of a fibrous substrate treated with
the fluorochemical urethane compounds. This fluorochemical urethane
compound(s) comprises the reaction product of (a) one or more
polyfunctional isocyanate compounds; (b) one or more hydrophilic
polyoxyalkylene compounds; (c) one or more fluorochemical
monofunctional compounds; and (d) one or more silane compounds.
[0045] Each fluorochemical urethane compound comprises a urethane
group that is derived or derivable from the reaction of at least
one polyfunctional isocyanate compound and at least one hydrophilic
polyoxyalkylene compound. The fluorochemical urethane compound is
terminated, on average, with (i) one or more perfluoroalkyl groups,
one or more perfluoroheteroalkyl groups; and (ii) one or more silyl
groups. It will be understood that the reaction product will
provide a mixture of compounds, some percentage of which will
comprise compounds as described, but may further comprise urethane
compounds having different substitution patterns and degree of
substitution.
[0046] In one preferred embodiment, the composition of the present
invention comprises 1) a mixture of urethane molecules arising from
the reaction of (a) one or more polyfunctional isocyanate
compounds, (b) one or more hydrophilic polyoxyalkylene compounds,
(c) one or more fluorochemical monofunctional compounds, and (d)
one or more silane compounds and 2) one or more auxiliary compounds
as described above.
[0047] Generally, the amount of said hydrophilic polyoxyalkylene
compound is sufficient to react with between 0.1 and 30% of
available isocyanate groups, the amount of said silanes is
sufficient to react with between 0.1 and 25% of available
isocyanate groups, and the amount of said fluorochemical
monofunctional compounds is sufficient to react with between 60 and
90% of available isocyanate groups. Preferably, the amount of said
hydrophilic polyoxyalkylene(s) is sufficient to react with between
5 and 30% of available isocyanate groups, the amount of said
silanes is sufficient to react with between 0.1 and 15% of
available isocyanate groups, and the amount of said fluorochemical
monofunctional compounds is sufficient to react with between 60 and
90% of available isocyanate groups.
[0048] Preferred classes of urethane compounds that may be present
are represented by the following formulas:
[0049]
R.sub.fZR.sup.2--X'(--CONH--Q(A).sub.m--NHCO--X'R.sup.3X'--).sub.nC-
ONH--Q(A)--NHCO--X'R.sup.1Si(Y).sub.3
[0050]
R.sub.fZR.sup.2--X'(--CONH--Q(A).sub.m--NHCO--X'R.sup.3X'--).sub.nC-
ONHR.sup.1Si(Y).sub.3
[0051] wherein:
[0052] R.sub.fZR.sup.2-- is a residue of at least one of the
fluorochemical monofunctional compounds;
[0053] R.sub.f is a perfluoroalkyl group having 2 to about 12
carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50
carbon atoms;
[0054] Z is a covalent bond, sulfonamido (--SO.sub.2NR--), or
carboxamido (--CONR--) where R is hydrogen or alkyl;
[0055] R.sup.1 is an alkylene, heteroalkylene, aralkylene, or
heteroaralkylene group;
[0056] R.sup.2 is a divalent straight or branched chain alkylene,
cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms,
preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon
atoms, and most preferably two carbon atoms, and preferably R.sup.2
is alkylene or heteroalkylene of 1 to 14 carbon atoms;
[0057] Q is a multi-valent organic group that is a residue of the
polyfunctional isocyanate compound;
[0058] R.sup.3 is a polyvalent, preferably divalent organic group
which is a residue of the hydrophilic polyoxyalkylene;
[0059] X' is --O--, --S--, or --N(R)--, wherein R is hydrogen or
C.sub.1-C.sub.4 alkyl;
[0060] each Y is independently a hydroxy; a hydrolyzable moiety
selected from the group consisting of alkoxy, acyloxy,
heteroalkoxy, heteroacyloxy, halo, and oxime; or a non-hydrolyzable
moiety selected from the group consisting of phenyl, alicyclic,
straight-chain aliphatic, and branched-chain aliphatic, wherein at
least one Y is a hydrolyzable moiety.
[0061] A is selected from the group consisting of
R.sub.fZR.sup.2--OCONH--- , (Y).sub.3SiR.sup.1XCONH--, and
(Y).sub.3SiR.sup.1NHCOOR.sup.3OCONH--.
[0062] m is an integer from 0 to 2; and
[0063] n is an integer from 1 to 10.
[0064] It will be understood with respect to the above formulas
that the compounds represent theoretical structures for the
reaction products. The reaction product will contain a mixture of
compounds in which the substitution patterns of the isocyanate
groups will vary.
[0065] Polyfunctional isocyanate compounds useful in the present
invention comprise isocyanate groups attached to the multivalent
organic group, Q, which can comprise a multivalent aliphatic,
alicyclic, or aromatic moiety; or a multivalent aliphatic,
alicyclic or aromatic moiety attached to a blocked isocyanate, a
biuret, an isocyanurate, or a uretdione, or mixtures thereof.
Preferred polyfunctional isocyanate compounds contain at least two
and preferably three or more --NCO groups. Compounds containing two
--NCO groups are comprised of divalent aliphatic, alicyclic,
araliphatic, or aromatic moieties to which the --NCO radicals are
attached. Preferred compounds containing three --NCO radicals are
comprised of isocyanatoaliphatic, isocyanatoalicyclic, or
isocyanatoaromatic, monovalent moieties, which are attached to a
biuret or an isocyanurate.
[0066] Representative examples of suitable polyfunctional
isocyanate compounds include isocyanate functional derivatives of
the polyfunctional isocyanate compounds as defined herein. Examples
of derivatives include, but are not limited to, those selected from
the group consisting of ureas, biurets, allophanates, dimers and
trimers (such as uretdiones and isocyanurates) of isocyanate
compounds, and mixtures thereof. Any suitable organic
polyisocyanate, such as an aliphatic, alicyclic, araliphatic, or
aromatic polyisocyanate, may be used either singly or in mixtures
of two or more.
[0067] The aliphatic polyfunctional isocyanate compounds generally
provide better light stability than the aromatic compounds, and are
preferred for treatment of fibrous substrates. Aromatic
polyfunctional isocyanate compounds, on the other hand, are
generally more economical and reactive toward hydrophilic
polyoxyalkylene compounds and other isocyanate-reactive compounds
than are aliphatic polyfunctional isocyanate compounds.
[0068] Suitable aromatic polyfunctional isocyanate compounds
include, but are not limited to, those selected from the group
consisting of 2,4-toluene diisocyanate (TDI), 2,6-toluene
diisocyanate, an adduct of TDI with trimethylolpropane (available
as Desmodur.TM. CB from Bayer Corporation, Pittsburgh, Pa.), the
isocyanurate trimer of TDI (available as Desmodur.TM. IL from Bayer
Corporation, Pittsburgh, Pa.), diphenylmethane 4,4'-diisocyanate
(MDI), diphenylmethane 2,4'-diisocyanate,
1,5-diisocyanato-naphthalene, 1,4-phenylene diisocyanate,
1,3-phenylene diisocyanate, 1-methyoxy-2,4-phenylene diisocyanate,
1-chlorophenyl-2,4-diisocyanate, and mixtures thereof.
[0069] Examples of useful alicyclic polyfunctional isocyanate
compounds include, but are not limited to, those selected from the
group consisting of dicyclohexylmethane diisocyanate (H.sub.12MDI,
commercially available as Desmodur.TM.W, available from Bayer
Corporation, Pittsburgh, Pa.),
4,4'-isopropyl-bis(cyclohexylisocyanate), isophorone diisocyanate
(IPDI), cyclobutane-1,3-diisocyanate, cyclohexane 1,3-diisocyanate,
cyclohexane 1,4-diisocyanate (CHDI), 1,4-cyclohexanebis(methylene
isocyanate) (BDI), 1,3-bis(isocyanatomethyl)cyclohexane
(H.sub.6XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl
isocyanate, and mixtures thereof.
[0070] Examples of useful aliphatic polyfunctional isocyanate
compounds include, but are not limited to, those selected from the
group consisting of 1,4-tetramethylene diisocyanate, hexamethylene
1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI),
1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene
diisocyanate (TMDI), 2,4,4-trimethyl-hexamethylene diisocyanate
(TMDI), 2-methyl-1,5-pentamethylene diisocyanate, dimer
diisocyanate, the urea of hexamethylene diisocyanate, the biuret of
hexamethylene 1,6-diisocyanate (HDI) (available as Desmodur.TM.
N-100 and N-3200 from Bayer Corporation, Pittsburgh, Pa.), the
isocyanurate of HDI (available as Demodur.TM. N-3300 and
Desmodurm.TM. N-3600 from Bayer Corporation, Pittsburgh, Pa.), a
blend of the isocyanurate of HDI and the uretdione of HDI
(available as Desmodur.TM. N-3400 available from Bayer Corporation,
Pittsburgh, Pa.), and mixtures thereof.
[0071] Examples of useful aryl aliphatic polyisocyanates include,
but are not limited to, those selected from the group consisting of
m-tetramethyl xylylene diisocyanate (m-TMXDI), p-tetramethyl
xylylene diisocyanate (p-TMXDI), 1,4-xylylene diisocyanate (XDI),
1,3-xylylene diisocyanate, p-(1-isocyanatoethyl)-phenyl isocyanate,
m-(3-isocyanatobutyl)-phenyl isocyanate,
4-(2-isocyanatocyclohexyl-methyl)-phenyl isocyanate, and mixtures
thereof.
[0072] Preferred polyisocyanates, in general, include those
selected from the group consisting of hexamethylene
1,6-diisocyanate (HDI), 1,12-dodecane diisocyanate isophorone
diisocyanate, toluene diisocyanate, dicyclohexylmethane
4,4'-diisocyanate, MDI, derivatives of all the aforementioned,
including Desmodur.TM. N-100, N-3200, N-3300, N-3400, N-3600, and
mixtures thereof.
[0073] Suitable commercially available polyfunctional isocyanates
are exemplified by Desmodur.TM. N-3200, Desmodur.TM. N-3300,
Desmodur.TM. N-3400, Desmodur.TM. N-3600, Desmodur.TM. H (HDI),
Desmodur.TM. W (bis[4-isocyanatocyclohexyl]methane), Mondur.TM. M
(4,4'-diisocyanatodiphenylmethane), Mondur.TM. TDS (98% toluene
2,4-diisocyanate), Mondur.TM. TD-80 (a mixture of 80% 2,4 and 20%
2,6-toluene diisocyanate isomers), and Desmodur.TM. N-100, each
available from Bayer Corporation, Pittsburgh, Pa.
[0074] Other useful triisocyanates are those obtained by reacting
three moles of a diisocyanate with one mole of a triol. For
example, toluene diisocyanate,
3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, or
m-tetramethylxylene diisocyanate can be reacted with
1,1,1-tris(hydroxymethyl)propane to form triisocyanates. The
product from the reaction with m-tetramethylxylene diisocyanate is
commercially available as CYTHANE 3160 (American Cyanamid,
Stamford, Conn.).
[0075] Hydrophilic polyoxyalkylene compounds suitable for use in
preparing the first component fluorochemical urethane compounds of
the present invention include those polyoxyalkylene compounds that
have an average functionality of greater than 1 (preferably, about
2 to 5; more preferably, about 2 to 3; most preferably, about 2, as
difunctional compounds such as diols are most preferred). The
isocyanate-reactive groups can be primary or secondary, with
primary groups being preferred for their greater reactivity.
Mixtures of compounds having different functionalities, for
examples mixtures of polyoxyalkylene compounds having one, two and
three isocyanate-reactive groups, may be used provide the average
is greater than 1. The polyoxyalkylene groups include those having
1 to 3 carbon atoms such as polyoxyethylene, polyoxypropylene, and
copolymers thereof such as polymers having both oxyethylene and
oxypropylene units.
[0076] Examples of polyoxyalkylene containing compounds include
alkyl ethers of polyglycols such as e.g. methyl or ethyl ether of
polyethylene glycol, hydroxy terminated methyl or ethyl ether of a
random or block copolymer of ethylene oxide and propylene oxide,
amino terminated methyl or ethyl ether of polyethyleneoxide,
polyethylene glycol, polypropylene glycol, a hydroxy terminated
copolymer (including a block copolymer) of ethylene oxide and
propylene oxide, a mono- or diamino-terminated poly(alkylene oxide)
such as Jeffamine.TM. ED, Jeffamine.TM. EDR-148 and
poly(oxyalkylene) thiols. Commercially available aliphatic
polyisocyanates include Baygard.TM. VP SP 23012, Rucoguard.TM. EPF
1421 and Tubicoat.TM. Fix ICB.
[0077] Useful commercially available hydrophilic polyoxyalkylene
compounds for the first component include Carbowax.TM.
poly(ethylene glycol) materials in the number average molecular
weight (M.sub.n) range of from about 200 to about 2000 (available
from Union Carbide Corp.); poly(propylene glycol) materials such as
PPG-425 (available from Lyondell Chemicals); block copolymers of
poly(ethylene glycol) and poly(propylene glycol) such as
Pluronic.TM. L31 (available from BASF Corporation); the "PeP"
series (available from Wyandotte Chemicals Corporation) of
polyoxyalkylene tetrols having secondary hydroxyl groups, for
example, "PeP" 450, 550, and 650.
[0078] Fluorochemical monofunctional compounds suitable for use in
preparing the chemical compositions of the present invention
include those that comprise at least one R.sub.f group. The R.sub.f
groups can contain straight chain, branched chain, or cyclic
fluorinated alkylene groups or any combination thereof. The R.sub.f
groups can optionally contain one or more heteroatoms (i.e. oxygen,
sulfur, and/or nitrogen) in the carbon-carbon chain so as to form a
carbon-heteroatom-carbon chain (i.e. a heteroalkylene group).
Fully-fluorinated groups are generally preferred, but hydrogen or
chlorine atoms can also be present as substituents, provided that
no more than one atom of either is present for every two carbon
atoms. It is additionally preferred that any R.sub.f group contain
at least about 40% fluorine by weight, more preferably at least
about 50% fluorine by weight. The terminal portion of the group is
generally fully-fluorinated, preferably containing at least three
fluorine atoms, e.g., CF.sub.3O--, CF.sub.3CF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2--, (CF.sub.3).sub.2N--,
(CF.sub.3).sub.2CF--, SF.sub.5CF.sub.2--. Perfluorinated aliphatic
groups (i.e., those of the formula C.sub.nF.sub.2n+1--) wherein n
is 2 to 12 inclusive are the preferred R.sub.f groups, with n=3 to
5 being more preferred and with n=4 being the most preferred.
[0079] Useful fluorochemical monofunctional compounds include
compounds of the following formula:
R.sub.f--Z--R.sup.2--X
[0080] wherein:
[0081] R.sub.f is a perfluoroalkyl group or a perfluoroheteroalkyl
group as defined above;
[0082] Z is a connecting group selected from a covalent bond, a
sulfonamido group, a carboxamido group, a carboxyl group, or a
sulfonyl group; and
[0083] R.sup.2 is a divalent straight or branched chain alkylene,
cycloalkylene, or
[0084] heteroalkylene group of 1 to 14 carbon atoms, preferably 1
to 8 carbon atoms,
[0085] more preferably 1 to 4 carbon atoms, and most preferably two
carbon atoms, and
[0086] X is an isocyanate-reactive functional groups, for example
--NH.sub.2; --SH; --OH; --N.dbd.C.dbd.O; or --NRH where R is H or a
C.sub.1C.sub.4 alkyl.
[0087] Representative examples of useful fluorochemical
monofunctional compounds include the following:
1 CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH.sub.2CH.sub- .2OH,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH(CH.sub.3)CH.sub.2OH,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH.sub.2CH(CH.sub.3)NH.su-
b.2,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2SH-
,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2SCH.su-
b.2CH.sub.2OH,
C.sub.6F.sub.13SO.sub.2N(CH.sub.3)(CH.sub.2).sub.4OH,
CF.sub.3(CF.sub.2).sub.7SO.sub.2N(H)(CH.sub.2).sub.3OH,
C.sub.3F.sub.7SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OH,
CF.sub.3(CF.sub.2).sub.4SO.sub.2N(CH.sub.3)(CH.sub.2).sub.4NH.sub.2,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)(CH.sub.2).sub.11OH,
CF.sub.3(CF.sub.2).sub.5SO.sub.2N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2OH,
CF.sub.3(CF.sub.2).sub.5SO.sub.2N(C.sub.2H.sub.5)(CH.sub.2).sub.6OH,
CF.sub.3(CF.sub.2).sub.2SO.sub.2N(C.sub.2H.sub.5)(CH.sub.2).sub.4OH,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(C.sub.3H.sub.7)CH.sub.2OCH.sub.2CH.sub.-
2CH.sub.2 OH, CF.sub.3(CF.sub.2).sub.4SO.sub.2N(CH.sub.2CH.-
sub.2CH.sub.3)CH.sub.2CH.sub.2OH,
CF.sub.3(CF.sub.2).sub.4SO.sub.2N(CH.sub-
.2CH.sub.2CH.sub.3)CH.sub.2CH.sub.2N HCH.sub.3,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(C.sub.4H.sub.9)CH.sub.2CH.sub.2NH.sub.2-
,
CF.sub.3(CF.sub.2).sub.3SO.sub.2N(C.sub.4H.sub.9)(CH.sub.2).sub.4SH,
CF.sub.3(CF.sub.2).sub.3CH.sub.2CH.sub.2OH
C.sub.4F.sub.9OC.sub.2F.sub-
.4OCF.sub.2CH.sub.2OCH.sub.2CH.sub.2OH;
n-C.sub.6F.sub.13CF(CF.sub.- 3)CON(H)CH.sub.2CH.sub.2OH;
C.sub.6F.sub.13CF(CF.sub.3)CO.sub.2C.sub.2H.su- b.4CH(CH.sub.3)OH;
C.sub.3F.sub.7CON(H)CH.sub.2CH.sub.2OH;
C.sub.3F.sub.7O(CF(CF.sub.3)CF.sub.2O).sub.1-
.sub.36CF(CF.sub.3)CH.sub.2OH;
[0088] and the like, and mixtures thereof. If desired, other
isocyanate-reactive functional groups may be used in place of those
depicted.
[0089] Silane compounds suitable for use in the chemical
compositions of the present invention are those of the following
formula:
X--R.sup.1--Si--(Y).sub.3
[0090] wherein X, R.sup.1, and Y are as defined previously.
Therefore, these silane compounds contain one, two, or three
hydrolysable groups (Y) on the silicon and one organic group
including an isocyanate-reactive or an active hydrogen reactive
radical (X--R.sup.1). Any of the conventional hydrolysable groups,
such as those selected from the group consisting of alkoxy,
acyloxy, heteroalkoxy, heteroacyloxy, halo, oxime, and the like,
can be used as the hydrolyzable group (Y). The hydrolysable group
(Y) is preferably alkoxy or acyloxy and more preferably alkoxy.
[0091] When Y is halo, the hydrogen halide liberated from the
halogen-containing silane can cause polymer degradation when
cellulose substrates are used. When Y is an oxime group, lower
oxime groups of the formula --N.dbd.CR.sup.5R.sup.6, wherein
R.sup.5 and R.sup.6 are monovalent lower alkyl groups comprising
about 1 to about 12 carbon atoms, which can be the same or
different, preferably selected from the group consisting of methyl,
ethyl, propyl, and butyl, are preferred.
[0092] Representative divalent bridging radicals (R.sub.1) include,
but are not limited to, those selected from the group consisting of
--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2C.sub.6H- .sub.4CH.sub.2CH.sub.2--, and
--CH.sub.2CH.sub.2O(C.sub.2H.sub.4O).sub.2CH-
.sub.2CH.sub.2N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2--.
[0093] Other preferred silane compounds are those which contain one
or two hydrolyzable groups, such as those having the structures
R.sup.2OSi(R.sup.7).sub.2R.sup.1XH and
(R.sup.8O).sub.2Si(R.sup.7)R.sup.1- XH, wherein R.sup.1 is as
previously defined, and R.sup.7 and R.sup.8 are selected from the
group consisting of a phenyl group, an alicycylic group, or a
straight or branched aliphatic group having from about 1 to about
12 carbon atoms. Preferably, R.sup.7 and R.sup.8 are a lower alkyl
group comprising 1 to 4 carbon atoms.
[0094] Following the hydrolysis of some of these terminal silyl
groups, inter-reaction with a substrate surface comprising --SiOH
groups or other metal hydroxide groups to form siloxane or
metal-oxane linkages, e.g., 1
[0095] can occur. Bonds thus formed, particularly Si--O--Si bonds,
are water resistant and can provide enhanced durability of the
stain-release properties imparted by the chemical compositions of
the present invention.
[0096] Such silane compounds are well known in the art and many are
commercially available or are readily prepared. Representative
isocyanate-reactive silane compounds include, but are not limited
to, those selected from the group consisting of:
2 H.sub.2NCH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3- ;
H.sub.2NCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3;
H.sub.2NCH.sub.2CH.sub.2CH.sub.2Si(O--N.dbd.C(CH.sub.3)(C.sub.2H.sub.5)).-
sub.3 HSCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3;
HO(C.sub.2H.sub.4O).sub.3C.sub.2H.sub.4N(CH.sub.3)(CH.sub.2).sub.3Si(OC.s-
ub.4H.sub.9).sub.3;
H.sub.2NCH.sub.2C.sub.6H.sub.4CH.sub.2CH.sub.2Si(OCH.s-
ub.3).sub.3; HSCH.sub.2CH.sub.2CH.sub.2Si(OCOCH.sub.3).sub.3;
HN(CH.sub.3)CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3;
HSCH.sub.2CH.sub.2CH.sub.2SiCH.sub.3(OCH.sub.3).sub.2;
(H3CO).sub.3SiCH.sub.2CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2CH.sub.2
Si(OCH.sub.3).sub.3; HN(CH.sub.3)C.sub.3H.sub.6Si(OCH.sub.3).sub.3-
; CH.sub.3CH.sub.2OOCCH.sub.2CH(COOCH.sub.2CH.sub.3)HNC.sub.3
H.sub.6Si(OCH.sub.2CH.sub.3).sub.3; C.sub.6H.sub.5NHC.sub.3H.sub.6-
Si(OCH.sub.3).sub.3;
H.sub.2NC.sub.3H.sub.6SiCH.sub.3(OCH.sub.2CH.sub.3).s- ub.2;
HOCH(CH.sub.3)CH.sub.2OCONHC.sub.3H.sub.6Si(OCH.sub.2CH.sub.3-
).sub.3;
(HOCH.sub.2CH.sub.2).sub.2NCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.2CH-
.sub.3).sub.3
H.sub.2NCH.sub.2CH.sub.2NHCH.sub.2CH.sub.2CH.sub.2Si(-
OC.sub.2H.sub.5).sub.3
H.sub.2NCH.sub.2CH.sub.2NHCH.sub.2CH.sub.2CH.sub.2S-
i(OCH.sub.3).sub.3
[0097] and mixtures thereof.
[0098] The chemical compositions of the present invention may be
made according to the following step-wise synthesis. As one skilled
in the art would understand, the order of the steps is non-limiting
and can be modified so as to produce a desired chemical
composition. In the synthesis, the polyfunctional isocyanate
compound and the monofunctional fluorochemical compound are
dissolved together under dry conditions, preferably in a solvent,
and then heating the resulting solution at approximately 40 to
80.degree. C., preferably approximately 60 to 70.degree. C., with
mixing in the presence of a catalyst for one-half to two hours,
preferably one hour. Depending on reaction conditions (e.g.,
reaction temperature and/or polyfunctional isocyanate used), a
catalyst level of up to about 0.5 percent by weight of the
polyfunctional isocyanate/polyoxyalkylene mixture may be used, but
typically about 0.00005 to about 0.5 percent by weight is required,
0.02 to 0.1 percent by weight being preferred.
[0099] Suitable catalysts include, but are not limited to, tertiary
amine and tin compounds. Examples of useful tin compounds include
tin II and tin IV salts such as stannous octanoate, dibutyltin
dilaurate, dibutyltin diacetate, dibutyltin di-2-ethylhexanoate,
and dibutyltinoxide. Examples of useful tertiary amine compounds
include triethylamine, tributylamine, triethylenediamine,
tripropylamine, bis(dimethylaminoethyl) ether, morpholine compounds
such as ethyl morpholine, and 2,2'-dimorpholinodiethyl ether,
1,4-diazabicyclo[2.2.2]octane (DABCO, Aldrich Chemical Co.,
Milwaukee, Wis.), and 1,8-diazabicyclo[5.4.0.]undec- -7-ene (DBU,
Aldrich Chemical Co., Milwaukee, Wis.). Tin compounds are
preferred.
[0100] The resulting fluorochemical functional urethane compounds
and compounds are then further reacted with one or more of the
silane compounds described above. The silane compound is added to
the above reaction mixture, and reacts with a substantial portion
of the remaining NCO groups. The above temperatures, dry
conditions, and mixing are continued one-half to two hours,
preferably one hour. Terminal silane-containing groups are thereby
bonded to the isocyanate functional urethane compounds.
Aminosilanes are preferred, because of the rapid and complete
reaction that occurs between the remaining NCO groups and the
silane compound's amino groups. Isocyanato functional silane
compounds may be used and are preferred when the ratio of
polyfunctional isocyanate compound to the hydrophilic difunctional
polyoxyalkylene and fluorochemical monofunctional compound is such
that the resulting compound has a terminal hydroxyl group.
[0101] These compounds are further functionalized with
polyoxyalkylene compounds, having an average functionality of
greater than 1, described above by reacting any of the remaining
NCO groups in the resulting mixture with one or more of the
reactive polyoxyalkylene compounds described above. Thus, the
polyoxyalkylene compound(s) is (are) added to the reaction mixture,
using the same conditions as with the previous additions.
[0102] The coating composition of the invention further comprises a
second auxiliary compound that is capable of improving the
durability of the repellency/resistant/release properties. In
particular, the second component improves the stain release in
general and the durability of the soil release. The auxiliary
compounds are generally non-fluorinated organic compounds and are
also called extenders hereinafter. Suitable extenders capable of
improving the oil- and/or water repellency properties include for
example blocked isocyanates including aromatic and aliphatic
blocked isocyanates, aliphatic polyisocyanates and aromatic or
aliphatic carbodiimides including aromatic or aliphatic
polycarbodiimides. Auxiliary compounds that are capable of
enhancing the soil/stain release properties are generally
non-fluorinated organic compounds such as for example blocked
isocyanate compounds that include a polyoxyalkylene group, in
particular a polyoxyethylene group. Auxiliary compounds that are
generally capable of improving durability of the repellency
properties or soil/stain release properties include non-fluorinated
organic compounds that have one or more groups (or a precursor
thereof) capable of reacting with the surface of the fibrous
substrate. Examples thereof include compounds that have isocyanate
groups or blocked isocyanates as described herein.
[0103] Polyisocyanates useful in preparing the second component
extender include those previously described for the first
component. In particularly, the previously described aliphatic
isocyanates are preferred due to their better light stability.
[0104] The aliphatic polyisocyanate for use in the second component
as an extender in the fluorochemical composition is preferably a
compound having a molecular weight of at least 350 g/mole. The
amount of free isocyanate groups in the aliphatic isocyanate is
typically at least 10% by weight of the total weight of the
compound, preferably at least 20% by weight. Suitable low molecular
weight aliphatic isocyanates include diisocyanates, triisocyanates
and mixtures thereof. Examples include hexamethylenediisocyanate,
2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and
1,2-ethylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate,
aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate,
cyclic trimer of hexamethylenediisocyanate and cyclic trimer of
isophorone diisocyanate (isocyanurates).
[0105] The polyoxyalkylene compound is generally reacted with the
aliphatic polyisocyanate in the presence of a catalyst such as an
organic tin compound and under reaction conditions commonly
employed. Polyoxyalkylene compounds useful in preparing the second
component extender include those previously described for the first
component. However, the polyoxyalkylene component preferably has a
functionality of less than two and is more preferably one. Mixtures
of polyoxyalkylene compounds having different degrees of
functionality may be used, provided that the average functionality
is less than two. Useful functional groups include any group that
is reactive toward the isocyanate groups of the second component
polyisocyanate, for example --NH.sub.2; --SH; --OH;
--N.dbd.C.dbd.O; or --NRH, where R is a lower alkyl. Monofunctional
polyoxyalkylene compounds are preferred.
[0106] The amount of polyoxyalkylene compound will be selected such
as to leave a desired amount of isocyanate groups unreacted.
Generally the amount of polyoxyalkylene compound is such that from
about 25 to about 75%, preferably 25 to 40% of the available
isocyanate groups are reacted. The remaining isocyanate groups may
be free isocyanate groups or may be preferably blocked isocyanate
groups. The resultant reaction mixture can be used in compositions
of the invention.
[0107] The polyoxyalkylene groups include those having 1 to 3
carbon atoms such as polyoxyethylene, polyoxypropylene,
polyoxytetramethylene and copolymers thereof such as polymers
having both oxyethylene and oxypropylene units. The polyoxyalkylene
containing organic compound may include one or two functional
groups such as hydroxy or amino groups. Examples of polyoxyalkylene
containing compounds include alkyl ethers of polyglycols such as
e.g. methyl or ethyl ether of polyethyleneglycol, hydroxy
terminated methyl or ethyl ether of a random or block copolymer of
ethyleneoxide and propyleneoxide, amino terminated methyl or ethyl
ether of polyethyleneoxide, polyethylene glycol, polypropylene
glycol, a hydroxy terminated copolymer (including a block
copolymer) of ethyleneoxide and propylene oxide, a diamino
terminated poly(alkylene oxide) such as Jeffamine.TM. ED,
Jeffamine.TM. EDR-148 and poly(oxyalkylene) thiols. Commercially
available aliphatic polyisocyanates include Baygard.TM. VP SP
23012, Rucoguard.TM. EPF 1421 and Tubicoat.TM. Fix ICB.
[0108] A "blocked isocyanate" is a polyisocyanate of a portion of
the isocyanate groups have been reacted with a blocking agent.
Isocyanate blocking agents are compounds that upon reaction with an
isocyanate group yield a group that is unreactive at room
temperature with compounds that at room temperature normally react
with an isocyanate but which group at elevated temperature reacts
with isocyanate reactive compounds. Generally, at elevated
temperature the blocking group will be released from the blocked
polyisocyanate group thereby generating the isocyanate group again
which can then react with an isocyanate reactive group, such as may
be found on the surface of a fibrous substrate. Blocking agents and
their mechanisms have been described in detail in "Blocked
isocyanates III.: Part. A, Mechanisms and chemistry" by Douglas
Wicks and Zeno W. Wicks Jr., Progress in Organic Coatings, 36
(1999), pp. 14-172.
[0109] The blocked isocyanate may be aromatic, aliphatic, cyclic or
acyclic and is generally a blocked di- or triisocyanate or a
mixture thereof and can be obtained by reacting an isocyanate with
a blocking agent that has at least one functional group capable of
reacting with an isocyanate group. Preferred blocked isocyanates
are blocked polyisocyanates that, at a temperature of less than
150.degree. C., are capable of reacting with an isocyanate reactive
group, through deblocking of the blocking agent at elevated
temperature. Preferred blocking agents include arylalcohols such as
phenols, lactams such as .epsilon.-caprolactam,
.delta.-valerolactam, .gamma.-butyrolactam, oximes such as
formaldoxime, acetaldoxime, methyl ethyl ketone oxime,
cyclohexanone oxime, acetophenone oxime, benzophenone oxime,
2-butanone oxime or diethyl glyoxime. Further suitable blocking
agents include bisulfite and triazoles.
[0110] According to a particular embodiment of the invention, the
blocked polyisocyanate may comprise the condensation product of a
polyisocyanate, for example a di- or triisocyanate, a blocking
agent, and an polyoxyalkylene compound, the polyoxyalkylene
compound having one or more, preferably one, isocyanate reactive
groups such as a hydroxy, amino or thiol group. Examples of such
organic compounds include those described above. Particularly
preferred are blocked polyisocyanates that have a self-emulsifying
capability in water. The use of blocked isocyanate compounds are
particularly useful in fibrous substrate when co-applied with
permanent press treatments, which require elevated temperatures
during application.
[0111] Examples of polyisocyanates for preparing the blocked
polyisocyanates include di- or triisocyanates as well as mixtures
thereof. Specific examples are aromatic diisocyanates such as
4,4'-methylenediphenylenediisocyanate,
4,6-di-(trifluoromethyl)-1,3-benze- ne diisocyanate,
2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and
p-xylylene diisocyanate, 4,4'-diisocyanatodiphenylether,
3,3'-dichloro-4,4'-diisocyanatodiphenylmethane,
4,5'-diphenyldiisocyanate- , 4,4'-diisocyanatodibenzyl,
3,3'-dimethoxy-4,4'-diisocyanatodiphenyl,
3,3'-dimethyl-4,4'-diisocyanatodiphenyl,
2,2'-dichloro-5,5'-dimethoxy-4,4- '-diisocyanato diphenyl,
1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate,
4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene
diisocyanate, and 1,8-dinitro-2,7-naphthylene diisocyanate and
aromatic tri-isocyanates such as
polymethylenepolyphenylisocyanate.
[0112] Still further isocyanates that can be used for preparing a
blocked isocyanate include alicyclic diisocyanates such as
3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate;
3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphatic
diisocyanates such as 1,6-hexamethylenediisocyanate,
2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and
1,2-ethylenediisocyanate; aliphatic triisocyanates such as
1,3,6-hexamethylenetriisocyanate; aromatic tri-isocyanates such as
polymethylenepolyphenylisocyanate (PAPI); cyclic diisocyanates such
as isophorone diisocyanate (IPDI) and
dicyclohexylmethane-4,4'-diisocyanate. Also useful are isocyanates
containing internal isocyanate-derived moieties such as
biuret-containing tri-isocyanates such as that available from Bayer
as DESMODUR.TM. N-100, isocyanurate-containing tri-isocyanates such
as that available from Huls AG, Germany, as IPDI-1890, and
azetedinedione-containing diisocyanates such as that available from
Bayer as DESMODUR.TM. TT. Also, other di- or tri-isocyanates such
as those available from Bayer as DESMODUR.TM. L and DESMODUR.TM. W,
and tri-(4-isocyanatophenyl)-methane (available from Bayer as
DESMODUR.TM. R) are suitable.
[0113] Commercially available blocked aromatic polyisocyanates
include Baygard.TM. EDW available from Bayer Corp. and
Hydrophobol.TM. XAN available from Ciba-Geigy.
[0114] A still further class of extenders suitable for use with the
fluorochemical composition of this invention are hydrophilic
carbodiimides. Suitable carbodiimides have been described in for
example U.S. Pat. Nos. 4,668,726, 4,215,205, 4,024,178, 3,896,251,
WO 93/22282, U.S. Pat. Nos. 5,132,028, 5,817,249, 4,977,219,
4,587,301, 4,487,964, 3,755,242 and 3,450,562. Particularly
suitable carbodiimides for use in this invention include those
corresponding to the formula:
R.sup.1--[N.dbd.C.dbd.N--R.sup.3].sub.u--N.dbd.C.dbd.N--R.sup.2
[0115] wherein u has a value of 1 to 10, typically 1 or 2, R.sup.1
and R.sup.2 each independently represent a hydrocarbon group, in
particular a linear, branched or cyclic aliphatic group preferably
having 6 to 18 carbon atoms and R.sup.3 represents a divalent
linear, branched or cyclic aliphatic group.
[0116] Yet a further class of extenders that can be advantageously
used as the second component in a fluorochemical urethane treatment
composition of this invention include hydrophilic polymers of
acrylic and/or methacrylic monomers. Particular examples of such
polymers include homo- and copolymers of partial alkyl esters of
acrylic and methacrylic acid such as for example C.sub.1 to
C.sub.30 alkyl esters of acrylic acid. Such acrylates should have
sufficient free (unesterified) carboxyl groups to provide the
requisite hydrophilicity. Specific examples of such alkyl esters
include methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl
acrylate and lauryl acrylate. Specific examples of suitable
polymers include a homopolymer of methyl acrylate and a copolymer
of methyl acrylate and octadecyl acrylate. One particularly useful
product is FC-672.TM., an acrylate stainblocker available from the
3M Company
[0117] The ratio of the first component fluorochemical urethane
compound(s) to the second component auxiliary compound may be from
about 12:1 to 1:12 and is typically from about 3:1 to 6:1.
[0118] The treatment composition for fibrous substrates comprises a
solution of the chemical compositions of the present invention and
at least one solvent. When applied to fibrous substrates, the
treatment compositions impart stain-release characteristics and
exhibit durability (i.e. they resist being worn-off) when exposed
to wear and abrasion from use, cleaning, and the elements.
[0119] The chemical compositions of the present invention can be
dissolved in a variety of solvents to form coating compositions
suitable for use in coating the chemical compositions of the
present invention onto a substrate. Fibrous substrate treatment
compositions may contain from about 0.1 to about 50 weight percent
chemical composition. Preferably the chemical composition is used
in the coating composition at about 0.1 to about 10 weight percent,
most preferably from about 2 to about 4 weight percent.
[0120] Suitable solvents include water, alcohols, esters, glycol
ethers, amides, ketones, hydrocarbons, chlorohydrocarbons,
chlorocarbons, and mixtures thereof. Depending upon the substrate
to which the composition is being applied, water is the preferred
solvent because it does not raise any environmental concerns and is
accepted as safe and non-toxic.
[0121] The treatment compositions of the present invention can be
applied as to a wide variety of fibrous substrates resulting in an
article that displays durable stain-release properties. The article
of the present invention comprises a fibrous substrate having a
treatment derived from at least one solvent and a chemical
composition of the present invention. After application and curing
of the coating composition, the substrate displays durable
stain-release properties.
[0122] The treatment composition may also be applied to other
substrates including glass, ceramic, stone, metal, semi-porous
materials such as grout, cement and concrete, wood, paint,
plastics, rubber.
[0123] The treatment compositions of the present invention can be
applied to a wide variety of fibrous substrates including woven,
knit, and nonwoven fabrics, textiles, carpets, leather, and paper.
Substrates having nucleophilic groups, such as cotton are preferred
because they can bond to the silane groups and/or isocyanate groups
of the chemical compositions of the present invention, thereby
increasing durability of the fiber treatment. Any application
method known to one skilled in the art can be used including
spraying, dipping, immersion, foaming, atomizing, aerosolizing,
misting, flood-coating, and the like.
[0124] To impart release/repellency/resistance characteristics to a
fibrous substrate, the coating composition of the present invention
is applied to the substrate and is allowed to cure (i.e. dry), at
ambient or elevated temperature.
[0125] In order to affect treatment of the fibrous substrate the
fibrous substrate is contacted with the fluorochemical composition
of the invention. For example, the substrate can be immersed in the
fluorochemical treating composition. The treated substrate can then
be run through a padder/roller to remove excess fluorochemical
composition and dried or cured. The treated substrate may be dried
at room temperature by leaving it in air or may alternatively or
additionally be subjected to a heat treatment, for example, in an
oven. A heat treatment is typically carried out at temperatures
between about 50.degree. C. and about 190.degree. C. depending on
the particular system or application method used. In general, a
temperature of about 120.degree. C. to 170.degree. C., in
particular of about 150.degree. C. to about 170.degree. C. for a
period of about 20 seconds to 10 minutes, preferably 3 to 5
minutes, is suitable. Alternatively, the chemical composition can
be applied by spraying the composition on the fibrous substrate. An
ambient cure preferably takes place at approximately 15 to
35.degree. C. (i.e. ambient temperature) until dryness is achieved,
up to approximately 24 hours. With either heat-treatment or ambient
cure, the chemical composition can also form chemical bonds with
the substrate and between molecules of the chemical
composition.
[0126] The choice of either heat-treatment or ambient cure often
depends on the desired end-use. For consumer applications, where
the composition may be applied to household laundry or carpeting,
and ambient cure is desired. For industrial applications, where the
fibrous substrate, such as a textile might normally be exposed to
elevated temperatures during production, an elevated temperature
cure or heat-treatment may be desirable. Generally, those
composition containing blocked isocyanate groups are preferred
where a heat-treatment is encountered
[0127] The amount of the treating composition applied to the
fibrous substrate is chosen so that a sufficiently high level of
the desired properties are imparted to the substrate surface
without substantially affecting the look and feel of the treated
substrate. Such amount is usually such that the resulting amount of
the fluorochemical urethane composition on the treated fibrous
substrate will be between 0.05% and 5% by weight based on the
weight of the fibrous substrate, known as solids on fiber or SOF.
The amount that is sufficient to impart desired properties can be
determined empirically and can be increased as necessary or
desired.
[0128] Fibrous substrates that can be treated with the
fluorochemical composition include in particular textiles. The
fibrous substrate may be based on synthetic fibers, e.g. polyester,
polyamide and polyacrylate fibers or natural fibers, e.g. cellulose
fibers as well as mixtures thereof. The fibrous substrate may be a
woven as well as a non-woven substrate. Preferred substrates are
cellulosic materials such as cotton, rayon, TENCEL.TM. and blends
of cellulosic materials.
[0129] The resulting treated substrates derived from at least one
solvent and a chemical composition of the present invention, have
been found to be resist soils and/or stains and/or to release soils
and/or stains with simple washing methods. The cured treatments
have also been found to be durable and hence to resist being
worn-off due to wear and abrasion from use, cleaning, and the
elements.
[0130] The invention will now be further illustrated with reference
to the following examples without the intention to limit the
invention thereto. All parts and percentages are by weight unless
stated otherwise.
EXAMPLES
[0131]
3TABLE 1 Designation Material Availability/Preparation APTES
3-aminopropyltriethoxysilan- e; Sigma-Aldrich, Milwaukee, WI
NH.sub.2(CH.sub.2).sub.3Si(OC.sub.- 2H.sub.5).sub.3 APTMS
3-aminopropyltrimethoxysilane; Sigma-Aldrich
NH.sub.2(CH.sub.2).sub.3Si(OCH.sub.3).sub.3 BO 2-Butanone oxime;
Sigma-Aldrich CH.sub.3CH.sub.2C(.dbd.NOH)CH.sub.3 Ethyl acetate
CH.sub.3CO.sub.2C.sub.2H.sub.5 Sigma-Aldrich DBTDL Dibutyltin
dilaurate; Sigma-Aldrich [CH.sub.3(CH.sub.2).sub.3]Sn[-
CO.sub.2(CH.sub.2).sub.10CH.sub.3].sub.2 MeFBSE
N-methylperfluorobutanesulfonyl Made by reacting ethanol;
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OH
perfluorobutanesulfonyl fluoride with CH.sub.3NH.sub.2 and ethylene
chiorohydrin, essentially as described in Ex. 1 of U.S. Pat. No.
2,803,656 (Ahlbrecht, et al.) MIBK Methylisobutyl ketone;
Sigma-Aldrich (CH.sub.3).sub.2CHCH.sub.2C(- O)CH.sub.3 MPEG 350
CARBOWAX .TM. 350; Union Carbide, Danbury, CT Methoxypolyethylene
glycol (MW.sub.av = 350) MPEG 550 CARBOWAX .TM. 550; Union Carbide,
Danbury, CT Methoxypolyethylene glycol (MW.sub.av = 550) MPEG 750
CARBOWAX .TM. 750; Union Carbide, Danbury, CT Methoxypolyethylene
glycol (MW.sub.av = 750) MPEG 2000 CARBOWAX .TM. 2000; Union
Carbide, Danbury, CT Methoxypolyethylene glycol (MW.sub.av = 2000)
N100 DESMODUR .TM. N-100; eq wt = 191 Bayer Polyfunctional
isocyanate resin based on hexamethylene diisocyante N3300 DESMODUR
.TM. N-3300; eq wt = 194 Bayer, Pittsburgh, PA Polyfunctional
isocyanate resin based on hexamethylene diisocyanate PEG 1000
CARBOWAX .TM. 1000; Union Carbide Polyethylene glycol (MW.sub.av =
1000) PEG 1450 CARBOWAX .RTM. 1450; Union Carbide Polyethylene
glycol (MW.sub.av = 1450) PEG 3350 CARBOWAX .TM. 3350; Union
Carbide Polyethylene glycol (MW.sub.av = 3350) FC-672 Acrylate
Stain Blocker Minnesota Mining and Manufacturing, St Paul, MN
Fabrics
[0132] Fabrics tested included: 65/35 polyester/cotton woven twill
(8 ounces/yd.sup.2 basis wt; available from Avondale Mills,
Graniteville, S.C.), 50/50 polyester/cotton plain weave (6
ounces/yd.sup.2 basis wt; available from Reeves Brothers Inc.,
Spartanburg, S.C.), and 60/40 cotton/polyester pique knit (5
ounces/yd.sup.2 basis wt; available from Cleveland Mills, Lawndale,
N.C.).
[0133] Application & Testing of Compositions
[0134] Application of compositions to polyester/cotton woven
fabrics
[0135] A 65% polyester, 35% cotton twill fabric was dipped into a
bath of the diluted polymer and immediately sent through a nip. The
concentration of the bath is adjusted to produce a fabric that when
dry had a fluorochemical solids coating ranging from 0.2 to 0.45%
solids of the fabric total weight. The bath also contained a
glyoxal-type resin, PERMAFRESH.TM. ULF (Omnova Solutions, Inc.,
Chester, S.C.) at about 10% on the weight of the bath, a citric
acid activated magnesium chloride catalyst, CATALYST.TM. 531
(Omnova Solutions, Inc.) at about 2.5% on the weight of the bath,
and a nonionic surfactant, PAT-WET.TM. LF-55 (Yorkshire Pat-Chem
Inc., Greenville, S.C.), at about 0.1% on the weight of the bath.
The fabric was dried and cured for 10 minutes at 150.degree. C.
Various performance tests were run on the fabric.
[0136] Application of compositions to Cotton/polyester knit
fabric
[0137] Knit fabrics were treated in the same way as the woven
fabrics, with the exception that FREEREZ.TM. 845 (Noveon, Inc.,
Cleveland, Ohio), a pre-catalyzed glyoxal-type resin was used in
place of the resin and catalyst combination above at about 12% on
the weight of the bath.
[0138] Performance Test--Oil Repellency
[0139] This test measures the resistance of the treated fabric to
oil-based insults. A drop of one standard surface tension fluid (of
a series of 8, with decreasing surface tensions) is dropped on a
treated fabric. If after thirty seconds there is no wetting, the
next highest standard number fluid (next lowest surface tension) is
tested. When the lowest number fluid soaks into the fabric, the
next lower number is the rating. For example, the fabric will
receive a three rating, if the number four fluid wets the fabric. A
more detailed description of the test is written in the 3M
Protective Material Division's "Oil Repellency Test I" method
(Document # 98-0212-0719-0).
[0140] Performance Test--Water Repellency:
[0141] This test measures the resistance of the treated fibrous
substrates to water based challenges. A drop of one standard
surface tension fluid (of a series of 11, with decreasing surface
tensions, based on water and water/isopropyl alcohol mixtures where
100% water is a 0 rating and 100% IPA is a 10 rating ) is placed on
a treated fabric to form a bead. If after thirty seconds there is
no wetting, the next highest standard number fluid (next lowest
surface tension) is tested. When the lowest number fluid soaks into
the fabric, the next lower number is the rating. For example, the
fabric will receive a three rating, if the number four fluid wets
the fabric. A more detailed description of the test is written in
the 3M Protective Material Division's "Water Repellency Test II"
method (Document # 98-0212-0721-6).
[0142] Performance Test--Artificial Antisoiling
[0143] This test measures the resistance of the treated fibrous
substrates to water based challenges. Typically a 12 in by 18 in
sample of carpet is divided into three to six sections. One section
is left untreated as the control and the other are treated with a
protective finish and let dry at room temperature where T
is=or<100 degrees F and releative humidity is<50%. The
treated article is afixed in a drum filled with 40 ceramic pellets
half weighing 10 g and half weighing 20 g and 20 g of 3M standard
oily test soil (available from 3M Protective Materials Division
Product 41-4201-6292-1). The drum is rolled for 10 minutes and then
rolled the other opposite direction for 10 minutes. The carpet is
removed and vacuumed in two directions and the treated areas are
compared with an untreated area. Direct comparisons are made within
the same sample and are rated from 1 to 5 where 3 is untreated, 1
is more soiled and 5 is no significant soiling. A more detailed
description of the test is written in the AATC "Artificial
Antisoiling Test" method 123-1995.
[0144] Performance Test--Acid Stain Resistance
[0145] This test measures the resistance of the treated fibrous
substrates to red acid dye stain. Test Method AATCC TM 175-1998 was
followed.
[0146] Performance Test--Oil Repellency--Durability
[0147] The Oil Repellency Test was run on treated fabric that had
subsequently been washed for 5, 10, or 20, consecutive launderings,
followed by tumble drying, as described in the 3M Protective
Materials Division "Laboratory Laundering Procedures" for home
laundering simulation (Document # 98-0212-0703-4).
[0148] Performance Test--Stain Release
[0149] This test evaluates the release of forced-in oil-based
stains from the treated fabric surface during simulated home
laundering. Five drops of mineral oil, Stain K (Kaydol, Witco
Chemical Co.) are dropped onto the fabric surface in a single
puddle, and a separate puddle of 5 drops of MAZOLA.TM. corn oil,
Stain E, are dropped on the fabric, and in a third puddle, 5 drops
of dirty motor oil (3M Co.) are dropped onto the fabric. The
puddles are covered with glassine paper, and weighted with a
five-pound weight each for 60 seconds. The weights and glassine
paper are removed from the fabric. The fabric sample is hung for
15-60 minutes, and then washed and dried. Samples are evaluated
against a rating board, and assigned a number from 1 to 8. An 8
represents total removal of the stain, where 1 is a very dark
stain. A more detailed description of the test is written in the 3M
Protective Material Division's "Stain Release Test I" method
(Document # 98-0212-0725-7).
[0150] Performance Test--Stain Release--Durability
[0151] The Stain Release Test was run on treated fabric that had
subsequently been washed for, e.g., 5, 10, or 20, consecutive
launderings, followed by tumble drying, as described in the 3M
Protective Material Division's "Laboratory Laundering Procedures"
for home laundering simulation (Document # 98-0212-0703-4).
[0152] Performance Test--Fabric Absorbency
[0153] This test provides a rough index of fabric absorbency. A
drop of water is placed on the fabric surface, and the amount of
time it takes for that drop to absorb into the fabric, leaving a
matte, wet surface, is recorded. A more detailed description of the
test is written in the 3M Protective Material Division's "Fabric
Absorbency Test" method (Document # 98-0212-0710-9). Absorbency
time is also referred to as the wicking time. Wetting time is the
time from application of the water drop, until the first evidence
of darkening or wetting appears under the water drop, was also
recorded.
[0154] Preparation 1:
[0155] Fluorochemical urethane MeFBSE/N3300/PEG 1450/APTES A 1
liter flask was charged with of MeFBSE (58.89 g), DBTDL (3 drops;
.about.20 mg) and MIBK(237.0 g). The temperature of the stirred
mixture was raised to 60.degree. C. under a purge of dry nitrogen.
N3300 (40.0 g) was then slowly added, maintaining the temperature
between 60-65 C. Upon completion of the addition, the reaction
mixture was stirred for 1 hour at 60.degree. C. APTES (4.56 g) was
then added dropwise, keeping temperature of the reaction mixture
below 65.degree. C., and the reaction mixture was stirred for 30
minutes. Solid PEG 1450 (14.95 g) was added to the stirred mixture,
and the reaction was followed to completion via FTIR, as determined
by disappearance of the --NCO band at approximately 2289
wavenumbers.
[0156] Emulsification: To this vigorously stirred organic mixture
was slowly added DI water ( 944 g; @ 60.degree. C.). This
pre-emulsion mixture was then sonicated for 2 minutes. A rotary
evaporator connected to an aspirator was used to strip the MIBK
from the mixture. The resulting emulsion was 20-30% solids.
[0157] The method described in Preparation 1 was followed to
produce Preparations 2-11 and Comparative Preparation C1, using
equivalent weight ratios and substitutions of materials as listed
in Table 2.
4TABLE 2 Eq. Wt. Eq. Wt. of Eq. Wt. Preparation isocyanate Eq. Wt.
of aminosilane Eq. Wt. of glycol No. (type) MeFBSE (type) (type) 1
1.00 (N3300) 0.80 0.10 (APTES) 0.10 (PEG 1450) 1a 1.00 (N3300) 0.80
0.10 (APTMS) 0.10 (PEG 1450) 2 1.00 (N3300) 0.80 0.05 (APTES) 0.15
(PEG 1450) 3 1.00 (N3300) 0.70 0.15 (APTES) 0.15 (PEG 1450) 4 1.00
(N100) 0.80 0.05 (APTES) 0.15 (PEG 1450) 5 1.00 (N100) 0.80 0.10
(APTES) 0.10 (PEG 1450) 6 1.00 (N3300) 0.80 0.075 (APTMS) 0.125
(PEG 1450) 2a 1.00 (N3300) 0.80 0.05 (APTMS) 0.15 (PEG 1450) C1
1.00 (N3300) 0.80 -- 0.20 (PEG 1450) 7 1.00 (N3300) 0.80 0.05
(APTES) 0.15 (MPEG 350) 8 1.00 (N3300) 0.80 0.05 (APTMS) 0.15 (MPEG
550) 9 1.00 (N3300) 0.80 0.05 (APTMS) 0.15 (PEG 1000) 10 1.00
(N3300) 0.80 0.05 (APTMS) 0.15 (MPEG 2000) 11 1.00 (N3300) 0.80
0.05 (APTMS) 0.15 (PEG 3350)
Testing on Carpet
[0158] preparations 1-11 and Comparative Preparation C1 were
diluted to a 3% solids emulsion with DI water and applied to carpet
as an aerosolized spray (Blue Transition III virgin carpet
available from Shaw Industries, Dalton, Ga.) to net a 0.6
g/ft.sup.2 solids add-on. Results of static water repellency
(Performance Test--Water Repellency), static oil repellency
(Performance Test--Oil Repellency), antisoiling (Performance
Test--Anti-Soiling Resistance) and acid stain resistance testing
(Performance Test--Acid Stain Resistance) for Examples C1-C11 are
listed in Table 3.
5TABLE 3 Preparation Static Water Static Oil Anti- Acid Stain Ex
No. Repellency Repellency soiling Resistance C1 C1 4 4 3.5 3.5 C2 1
4 5 4.5 3.5 C3 2 4 4 4 3.5 C4 3 3 3 3.5 3.5 C5 4 2 2 4 3 C6 5 2 2 4
3 C7 6 4 4 4.5 3.5 C8 7 3 3 4.5 3.5 C9 8 2 3 4.5 3.5 C10 9 3 3 4.5
3.5 C11 10 1 2 3.5 3.5 C12 11 DI Water 2 3 3.5 C14 C3 None None 3 1
(untreated)
[0159] Test on fabrics:
[0160] Preparations 1-11 and Comparative Preparation C1, were
diluted to 4% solids emulsion with DI water and applied to
cotton/polyester 35/65 blend fabric (#7206 from Test Fabrics Inc.
Middlesex, N.J.) to yield a 0.8 g/ft.sup.2 add-on.
6TABLE 4 Static Water Static Oil Ex Preparation No. Repellency
Repellency Antisoiling C15 C1 3 4 3.5 C16 1 3 4 4.5 C17 2 3 4 4 C18
3 1 4 3.5 C19 4 1 2 4 C20 5 1 2 4 C21 6 3 5 4.5 C23 untreated 0 0
1
[0161] Preparation 12:
[0162] Blocked isocyanate extender N100/MPEG 750/BO
[0163] A 1 liter flask, equipped with a reflux condenser, a
mechanical stirrer, thermocouple and nitrogen inlet was charged
with N100 (95.5 g), ethyl acetate (250.0 g) and MPEG 750 (125.0 g).
To this stirred mixture was added DBTDL (0.25 g) and the ensuing
mixture was heated to 75.degree. C. and stirred overnight. The
mixture was then cooled to room temperature and BO (29.1 g) was
added dropwise with stirring. The mixture was heated to 75.degree.
C. and stirred overnight. DI water (750.0 g) was slowly added,
allowing the temperature to be held between 65.degree. C. and
75.degree. C. during addition. The mixture was homogenized using an
ultrasonic homogenizer (model CPX 600, available from Cole-Parmer,
Vernon Hills, Ill.) for five minutes. Ethyl acetate was removed by
distillation under reduced pressure. A hazy solution was
obtained.
[0164] Preparations 13-15
[0165] The procedure outlined above for Preparation 12 was followed
to make Preparation 13-15, with substitution of materials as
described in Table 5.
7TABLE 5 --NCO --OH BO Water Preparation % solids MPEG eqiv equiv
equiv equiv 13 31.1 550 1.00 0.33 0.67 0.00 14 30.5 750 1.00 0.33
0.38 0.29 15 31.7 2000 1.00 0.33 0.67 0.00
[0166] Table 5. Results of Preparations C1, 2 and 7 applied to
50/50 polyester/cotton plain weave fabric
8 TABLE 6 Pre- Solids Initial para- on Oil Ex tion fiber repellency
Wet Absorbency K E C C24 -- -- 0 0.5 30 5 5 3 C25 2 0.20 6 23 30
6.5 6 5.5 C26 C1 0.19 6 15 30 7 6.5 6 C27 2a 0.22 6 24.3 30 6.5 7
6.5
[0167] Table 6. Results of Preparations C1, 2 and 8 applied to
50/50 polyester cotton weave fabric; extended launderings (5, 10
and 20).
9 TABLE 7 Ex O/R Wet Absorbency K E C 5 Launderings C24 0 0.5 6.3 5
5 3 C25 3 13 30 6.5 6.5 5 C26 0 0.5 30 6.5 7 5 C27 3 18 30 6.5 6.5
6.5 10 Launderings C24 0 0.5 6.7 5 5 3 C25 1.5 2.3 30 6 7 6 C26 0
0.5 30 6 6.5 5 C27 1.5 1.3 30 6.5 7 5 20 Launderings C24 0 0.5 5.1
5 5 3 C25 0.5 1.3 30 6.5 6 4 C26 0 0.5 23 6 6 5 C27 1 0.5 30 6.5 6
4
[0168] Tables 6 and 7, example C-26, shows that without the silane,
no oil repellency is present at 5 launderings, where examples C-25
and C-27, with silane, show oil repellency durability to 20
launderings. Samples C-25 and C-27 show longer absorbency times
than C-26. Longer absorbency times are a measure of the resistance
of the fabric to wet-out by aqueous materials, e.g. water. In all
examples, stain release values were at least one point, or
significantly better than, the control example, C-24.
[0169] Table 8 Results of Preparation 7 (0.45% solids on fiber)
with various extenders on 60/40 cotton/polyester pique knit
fabric
10 TABLE 8 Ex- Initial C4 tender Absor- Ex Prep sof sof O/R Wet
bency K E C C-28 -- -- -- 0 0.5 0.5 5 6.5 3 C-29 2 0.453 4 1.7 30 7
7.5 6.5 1 2a & 13 0.453 0.53 4.5 2.7 30 7 7.5 7.5 2a 2a &
14 0.453 0.52 4.5 6.7 30 7.5 8 7.5 3 2a & 15 0.453 0.54 5 2.8
30 7.5 8 7.5
[0170] Table 9. Results of Preparation 2 applied to 60/40
cotton/polyester knit fabric; extended launderings (4, 8 and
12)
11 TABLE 9 Ex O/R Wet Absorbency K E C 4 Launderings C-28 0 0.5 0.5
5 6.5 3 C-29 0 1.1 30 6.5 7 6.5 1 0 2.2 30 7 7 7 2 0 1.2 27.1 7.5
7.5 7 3 0 1.3 30 7.5 7 7 8 Launderings C-28 0.5 0.5 5 6 3 C-29 0.5
30 6.5 7 6.5 1 1 30 6.5 7 6.5 2 1.2 27.8 7 7.5 7 3 0.5 5.8 6.5 7.5
6.5 12 Launderings C-28 0.5 0.5 5 6.5 3 C-29 0.5 30 6.5 6.5 5 1 0.5
30 6.5 6.5 6.5 2 0.5 30 7 7 6.5 3 0.5 5 7 7 6
[0171] Tables 8 & 9 show performance on a knitted substrate of
the fluorinated compound alone, C-29, and the performance of the
fluorinated compound with the various extender preparations, 1, 2,
3. In examples 1 and 2, extenders with MPEG 550 and 750
respectively, extended both the absorbency times, and the release
of Stain C, to at least 12 launderings. In example 3, use of an
extender with MPEG 2000, improved the release of Stain C. Overall,
stain release is shown to be improved by treatment with the
fluorinated and hydrocarbon extender in combination.
[0172] Table 10 Results of Preparation 1 applied at 0.29% solids on
fiber to 65/35 Polyester/Cotton twill fabric with various
extentenders.
12 TABLE 10 Ex Preparation C4 sof Extender sof C-30 -- -- -- C-31 1
0.289 -- 4 1a & 13 0.289 0.44 5 1a & 14 0.289 0.43 6 1a
& 15 0.289 0.45
[0173] Table 11 Results of Preparation 1 applied at 3% to 65/35
Polyester/cotton twill fabric initial, 5 and 10 launderings
13 TABLE 11 Absor- Ex O/R Wet bency K E C Initial C-30 0 0.5 3.1 6
6 4 C-31 6 30 30 7 7 4 4 6 30 30 7.5 7.5 7 5 6 30 30 7.5 7 7 6 6 30
30 7.5 7.5 7 5 Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 5 30 30 7
6.5 3 4 5 30 30 7.5 7 6.5 5 4 30 30 7.5 7 6.5 6 2 10.8 30 7.5 7 7
10 Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 4 30 30 7 6.5 3 4 3.5 30
30 7 7 5 5 2 30 30 7.5 7 6 6 1.5 1.9 30 7.5 7 6.5
[0174] Table 12. Results of Preparation 1 applied at 3% to 65/35
Polyester/cotton twill fabric 20, 25 and 30 launderings
14 TABLE 12 O/R Wet Absorbency K E C 20 Launderings C-30 0 0.5 0.5
6 6 4 C-31 2 11.1 30 7 7 3 4 2 2.3 30 6.5 7 6.5 5 1 9.2 30 7 7 6 6
0 0.5 11.7 7.5 7 7 25 Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 2 4.5
30 7 6.5 2.5 4 1.5 4.2 30 7 7 6 5 0.5 1.6 30 7 6.5 6 6 0 0.5 10.6
7.5 7.5 7 30 Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 1.5 4.1 30 7
6.5 2.5 4 1 2.5 30 7 6.5 6 5 0.5 1.6 30 7 6.5 6 6 0 0.5 2.8 7.5 7.5
7
[0175] Tables 10, 11, and 12 demonstrate performance of the various
preparations on yet another fabric, 65/35 polyester/cotton twill.
Anti-absorbency benefits of extender preparations 13 and 14 are
again demonstrated in examples 4 and 5. All extender examples, 4, 5
and 6 show significant improvements in release of Stain C in as
many as 30 home launderings. Again, on average, stain release is
improved with the combination of the hydrocarbon extender and
fluorochemical compound.
[0176] Table 13 shows that curing compositions at ambient
conditions (7) will provide stain release benefits to fabrics over
controls (C-32, C-33).
15 TABLE 13 Prepara- Cure Initial Ex tion C4 sof Extender sof Temp
O/R K E C C-32 -- -- -- RT 0 6 6 4 C-33 -- -- -- 300 F. 0 6 6 4 7 6
& 15 0.56 0.16 RT 0 6.5 7 6 8 6 & 15 0.56 0.16 150 F. 1 7 7
6 9 6 & 15 0.56 0.16 200 F. 5 7 8 6.5 10 6 & 15 0.56 0.16
250 F. 5 7.5 7.5 7 11 6 & 15 0.56 0.16 300 F. 5 7 7.5 7.5
* * * * *